Highlights 2010

In the past decade, Resonant Inelastic X-ray Scattering (RIXS) has made remarkable
progress as a spectroscopic technique. This is a direct result of the availability of high brilliance
synchrotron X-ray radiation sources and of advanced photon detection instrumentation.
The technique's unique capability to probe elementary excitations in complex
materials by measuring their energy-, momentum-, and polarization-dependence
has brought RIXS to the forefront of experimental photon science. We review both
the experimental and theoretical RIXS investigations of the past decade, focusing on
those determining the low-energy charge, spin, orbital and lattice excitations of solids.
We present the fundamentals of RIXS as an experimental method and then review the
theoretical state of aaffirs, its recent developments and discuss the different (approximate)
methods to compute the dynamical RIXS response. The last decade's body of
experimental RIXS data and its interpretation is surveyed, with an emphasis on RIXS
studies of correlated electron systems, especially transition metal compounds. Finally,
we discuss the promise that RIXS holds for the near future, particularly in view of the
advent of x-ray laser photon sources.

Phonons, the quantum mechanical representation of lattice vibrations, and their coupling to the electronic degrees of freedom are important for understanding thermal and electric properties of materials. For the first time, phonons have been
measured using resonant inelastic x-ray scattering (RIXS) across the Cu K-edge in cupric oxide (CuO). Analyzing these spectra using an ultra-short core-hole lifetime approximation and exact diagonalization techniques, we can explain the essential inelastic features. The relative spectral intensities are related to the electron-phonon coupling strengths.

The electronic structure and magnetism of Ir 5d5 states in non-metallic, weakly ferromagnetic
BaIrO3 is probed with x-ray absorption techniques. Contrary to expectation the Ir 5d orbital
moment is found to be ~1.5 times larger than the spin moment. This unusual, atomic-like nature of
the 5d moment is driven by a strong spin-orbit interaction in heavy Ir ions, as confirmed by the nonstatistical
large branching ratio at Ir L2/3 absorption edges. As a consequence, orbital interactions
cannot be neglected when addressing the nature of magnetic ordering in BaIrO3. The local moment
behavior persists even as the metallic/paramagnetic phase boundary is approached with Sr doping
or applied pressure.

Crystallographic analysis of x-ray and neutron diffraction data is a widely used technique to provide three-dimensional (3-D) pictures of how atoms are arranged in materials, an essential first step toward understanding a material’s function. Computer software is an indispensable part of the crystallographic analysis process. A recent citation milestone demonstrates the great contribution to science that is made by a pair of such programs authored by two Argonne scientists.

The mechanism behind fast intersystem crossing in transition-metal complexes is shown to be a result of the dephasing of the photoexcited state to the phonon continuum of a different state with a significantly different transition metal-ligand distance. The coupling is a result of the spin-orbit interaction causing a change in the local moment. A recurrence to the initial state is prevented by the damping of the phonon oscillation. The decay time is faster than the oscillation frequency of the transition metal-ligand stretch mode, in agreement with experiment. For energies above the region where the strongest coupling occurs, a slower ''leakage-type'' decay is observed. If the photoexcited state is lower in energy than the state it couples to, then there is no decay.

We report how ultrathin MgO films on Ag(001) surfaces can be used to control the emittance properties of photocathodes. In addition to substantially reducing the work function of the metal surface, the MgO layers also favorably influence the shape of the surface bands resulting in the generation of highbrightness electron beams. As the number of MgO surface layers varies from 0 to 3, the emitted electron
beam becomes gradually brighter, reducing its transverse emittance to 0:06 mm mrad. We suggest the use of such photocathodes for the development of free-electron x-ray lasers and energy-recovery linac x-ray sources.

We investigate the cascade decay mechanism for ultrafast intersystem crossing mediated by the spin-orbit coupling in transition-metal complexes. A quantum-mechanical description of the cascading process that occurs after photoexcitation is presented. The conditions for ultrafast cascading are given, which relate the energy difference between the levels in the cascading process to the electron-phonon self energy. These limitations aid in the determination of the cascade path. For Fe2+ spin-crossover complexes, this leads to the conclusion that the ultrafast decay primarily occurs in the manifold of antibonding metal-to-ligand charge-transfer states. We also give an interpretation why some intermediate states are bypassed.